US20180257975A1 - Borosilicate glass for pharmaceutical container, glass tube for pharmaceutical container, and manufacturing method for pharmaceutical container - Google Patents

Borosilicate glass for pharmaceutical container, glass tube for pharmaceutical container, and manufacturing method for pharmaceutical container Download PDF

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Publication number
US20180257975A1
US20180257975A1 US15/757,155 US201615757155A US2018257975A1 US 20180257975 A1 US20180257975 A1 US 20180257975A1 US 201615757155 A US201615757155 A US 201615757155A US 2018257975 A1 US2018257975 A1 US 2018257975A1
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Prior art keywords
glass
pharmaceutical container
borosilicate glass
container according
smaller
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US15/757,155
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English (en)
Inventor
Miki Kimura
Shinsaku Nishida
Ken Choju
Takanori Iwasaki
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Nippon Electric Glass Co Ltd
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Nippon Electric Glass Co Ltd
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Priority claimed from JP2015173791A external-priority patent/JP2017048091A/ja
Priority claimed from JP2015181342A external-priority patent/JP2017057096A/ja
Priority claimed from JP2015207709A external-priority patent/JP6653076B2/ja
Application filed by Nippon Electric Glass Co Ltd filed Critical Nippon Electric Glass Co Ltd
Assigned to NIPPON ELECTRIC GLASS CO., LTD. reassignment NIPPON ELECTRIC GLASS CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CHOJU, KEN, IWASAKI, TAKANORI, KIMURA, MIKI, NISHIDA, SHINSAKU
Publication of US20180257975A1 publication Critical patent/US20180257975A1/en
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
    • A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
    • A61J1/05—Containers specially adapted for medical or pharmaceutical purposes for collecting, storing or administering blood, plasma or medical fluids ; Infusion or perfusion containers
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B15/00—Drawing glass upwardly from the melt
    • C03B15/14—Drawing tubes, cylinders, or rods from the melt
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B23/00—Re-forming shaped glass
    • C03B23/04—Re-forming tubes or rods
    • C03B23/09—Reshaping the ends, e.g. as grooves, threads or mouths
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
    • C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
    • C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/20—Compositions for glass with special properties for chemical resistant glass
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
    • A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
    • A61J1/05—Containers specially adapted for medical or pharmaceutical purposes for collecting, storing or administering blood, plasma or medical fluids ; Infusion or perfusion containers
    • A61J1/06—Ampoules or carpules
    • A61J1/065—Rigid ampoules, e.g. glass ampoules

Definitions

  • the present invention relates to borosilicate glass for a pharmaceutical container which is used for glass for a tubular bottle such as a vial or an ampule or a syringe of an injector, a glass tube for a pharmaceutical container, and a manufacturing method for a pharmaceutical container.
  • the following characteristics are necessary for the borosilicate glass for a pharmaceutical container such as a vial or an ampule.
  • a linear thermal expansion is low such that breakage due to thermal shock does not occur in a production process of a glass tube or at the time of converting process into a vial, an ampule and the like.
  • a quantity of heat at the time of converting process into a vial, an ampule and the like can be decreased so that an inner surface of a container is not deteriorated due to an evaporant from glass, after the converting process.
  • a standard borosilicate glass for a pharmaceutical container satisfying these required characteristics includes SiO 2 , B 2 O 3 , Al 2 O 3 , Na 2 O, K 2 O, CaO, BaO, and a small amount of a fining agent, as constituent components.
  • Patent Document 1 JP-A-2014-214084
  • aqueous-based medicaments present in the containers has proceeded and aqueous-based medicaments having higher medical efficacy have been used.
  • aqueous-based medicaments there is an aqueous-based medicament which is chemically unstable and easily denatured, and has high reactivity with glass.
  • a glass having higher chemical durability or hydrolytic resistance than those in the related art is required for a borosilicate glass for a pharmaceutical container such as a vial or an ampule.
  • a glass includes BaO
  • barium-feldspar crystals are easily precipitated and productivity is decreased due to a reaction with an alumina-based refractory at the time of glass melting, and Ba ions extracted from the glass may be reacted with sulfate ions in an aqueous-based medicament to generate an insoluble precipitate.
  • Patent Document 1 proposed is a glass having high hydrolytic resistance without including BaO.
  • a pharmaceutical container such as a vial or an ampule is manufactured by locally heating and converting tubular glass with a burner. At the time of performing the heating with a burner, B 2 O 3 or Na 2 O in the glass is evaporated and condensed on an inner surface of a pharmaceutical container, and a heterogeneous layer may be formed.
  • An object of the invention is to provide a borosilicate glass for a pharmaceutical container which has good processability in spite of not including BaO.
  • the inventors have carried out various experiments and found that, when a water content in a glass is high, absorption in an infrared region increases, and the quantity of heat at the time of converting process into a container can be reduced.
  • a borosilicate glass for a pharmaceutical container including SiO 2 , Al 2 O 3 , B 2 O 3 , and R 2 O (R is one or more kinds selected from Li, Na, and K) as essential components, in which BaO is not substantially included, and a water content in the glass is 0.30 to 0.80/mm in terms of ⁇ -OH value.
  • R is one or more kinds selected from Li, Na, and K
  • BaO is not substantially included
  • a water content in the glass is 0.30 to 0.80/mm in terms of ⁇ -OH value.
  • the expression of “BaO is not substantially included” means not positively adding BaO. It is not the gist of excluding BaO contaminated as impurities. More specifically, the expression of “BaO is not substantially included” means that a content of BaO is equal to or smaller than 0.05% in terms of mass %.
  • the glass absorbs infrared light emitted at the time of converting process into a container with a burner.
  • the glass can be efficiently heated, and as a result, it becomes possible to reduce quantity of heat required at the time of converting process into a container. Accordingly, an amount of B 2 O 3 , Na 2 O, or the like evaporated at the time of converting process into a container can be reduced and a pharmaceutical container in which a heterogeneous layer is hardly formed on an inner surface thereof can be obtained.
  • a term “quantity of heat” represents a quantity of heat supplied from flame of a burner, and corresponds to a sum of a quantity of heat that contributes to heating of the glass and a quantity of heat that contributes to heating of ones other than glass.
  • the borosilicate glass for a pharmaceutical container includes 70.0% to 75.5% of SiO 2 , 6.3% to 11% of Al 2 O 3 , 3.0% to 11.5% of B 2 O 3 , 4.0% to 8.5% of Na 2 O, 0% to 5.0% of K 2 O, and 0% to 0.2% of Li 2 O in terms of mass %.
  • each content of MgO, CaO, and SrO is 0 to 4 mass %.
  • MgO+CaO+SrO is 0 to 4 mass %.
  • the expression of “MgO+CaO+SrO” means a total content of MgO, CaO, and SrO.
  • MgO+CaO is equal to or greater than 0 and smaller than 1 mass %.
  • Na 2 O+K 2 O+Li 2 O is 5 to 10 mass %.
  • the expression of “Na 2 O+K 2 O+Li 2 O” means a total content of Na 2 O, K 2 O, and Li 2 O.
  • a content of Fe 2 O 3 is equal to or greater than 0 and smaller than 0.2 mass %.
  • a value of (MgO+CaO+SrO)/(Na 2 O+K 2 O+Li 2 O) is adjusted to be equal to or smaller than 0.10 in terms of mass ratio.
  • the expression of “(MgO+CaO+SrO)/(Na 2 O+K 2 O+Li 2 O)” represents a value that is obtained by dividing the total content of MgO, CaO, and SrO by the total content of Na 2 O, K 2 O, and Li 2 O.
  • CaO/(Na 2 O+K 2 O+Li 2 O) is 0 to 0.10 in terms of mass ratio.
  • the expression of “CaO/(Na 2 O+K 2 O+Li 2 O)” represents a value that is obtained by dividing a content of CaO by the total content of Na 2 O, K 2 O, and Li 2 O.
  • K 2 O/Na 2 O is 0.2 to 1.0 in terms of mass ratio.
  • the expression of K 2 O/Na 2 O represents a value obtained by dividing a content of K 2 O by a content of Na 2 O.
  • Al 2 O 3 /(Na 2 O+K 2 O+Li 2 O) is 0.7 to 1.5 in terms of mass ratio.
  • the expression of “Al 2 O 3 /(Na 2 O+K 2 O+Li 2 O)” represents a value that is obtained by dividing a content of Al 2 O 3 by the total content of Na 2 O, K 2 O, and Li 2 O.
  • a consumption of 0.02 mol/L hydrochloric acid per unit glass mass is equal to or smaller than 0.030 mL.
  • a weight loss per area is equal to or smaller than 1.0 mg/dm 2 .
  • a working temperature is 1150° C. to 1250° C.
  • the “working temperature” is a temperature at which a viscosity of the glass is 10 4 dPa ⁇ s.
  • a converting temperature at the time of manufacturing a glass container such as an ampule or a vial from a glass tube can be decreased and the amount of B 2 O 3 or an alkali metal oxide component evaporated from the glass can be significantly decreased.
  • the amount of B 2 O 3 or an alkali metal oxide component evaporated from the glass can be significantly decreased.
  • a liquidus viscosity is equal to or greater than 10 4.5 dPa ⁇ s.
  • a glass tube for a pharmaceutical container made of the borosilicate glass for a pharmaceutical container described above.
  • an amount of B 2 O 3 or Na 2 O evaporated has a relation with not only a composition or water content of a glass tube but also dimensional accuracy of the glass tube, and it is possible to reduce quantity of heat required for converting processing into a container by reducing a bend or thickness deviation of the glass tube and increasing processability.
  • a glass tube for a pharmaceutical container including a borosilicate glass in which the borosilicate glass including SiO 2 , Al 2 O 3 , B 2 O 3 , and R 2 O (R is one or more kinds selected from Li, Na, and K) as essential components, and substantially not including BaO, in which a bend of the glass tube is equal to or smaller than 6.0 mm, and a thickness deviation of the glass tube is equal to or smaller than 15%.
  • the expression “bend of a glass tube” means a bend per 1000 mm of tube length.
  • the thickness deviation indicates a value of (maximum thickness ⁇ minimum thickness)/target thickness, that is, the value is obtained by dividing the difference between a maximum and a minimum thickness of the glass tube by a target thickness and is expressed as a percentage.
  • the borosilicate glass includes 70.0% to 75.5% of SiO 2 , 6.3% to 11.0% of Al 2 O 3 , 3.0% to 11.5% of B 2 O 3 , 4.0% to 8.5% of Na 2 O, 0% to 5.0% of K 2 O, and 0% to 0.2% of Li 2 O in terms of mass %.
  • the inner surface of the container may be peeled off to cause generation of insoluble foreign materials, which are called flakes, in the aqueous-based medicament.
  • the glass tube of the related art has Na 2 O with high content in the vicinity of a surface, this fact is related to form the heterogeneous layer, and an increase in a content of Na 2 O is caused by extraction of Na 2 O component from refractory or the like used when forming a glass tube.
  • a glass tube for a pharmaceutical container including a borosilicate glass, in which the borosilicate glass includes SiO 2 , Al 2 O 3 , B 2 O 3 , and R 2 O (R is one or more kinds selected from Li, Na, and K) as essential components, and substantially does not include BaO, and a value of (atomic concentration of Na)/(atomic concentration of Na+atomic concentration of Si) in a region from an inner surface of the glass tube to a depth of 200 nm is equal to or greater than 0.01 and smaller than 0.5.
  • R is one or more kinds selected from Li, Na, and K
  • (atomic concentration of Na)/(atomic concentration of Na+atomic concentration of Si) indicates a value that is obtained by dividing the atomic concentration of Na by the sum of the atomic concentration of Na and the atomic concentration of Si, that is, the value is the maximum value in the region from the surface of the glass to a depth of 200 nm.
  • the concentration of Na 2 O in the vicinity of the surface is optimized, it is possible to prevent such as B 2 O 3 or Na 2 O in the glass from being evaporated at the time of performing heating with a burner, it is possible to prevent the heterogeneous layer from being formed.
  • the borosilicate glass includes 65% to 80% of SiO 2 , 5% to 15% of Al 2 O 3 , 2% to 12% of B 2 O 3 , 3% to 10% of Na 2 O, 0% to 5% of K 2 O, 0% to 5% of Li 2 O, 0% to 5% of MgO, 0% to 5% of CaO, and 0% to 5% of SrO in terms of mass %, and a value of Al 2 O 3 /(Na 2 O+K 2 O+Li 2 O+MgO+CaO+SrO+B 2 O 3 ) is 0.35 to 0.60 in terms of mass ratio.
  • a pharmaceutical container made of the borosilicate glass for a pharmaceutical container described above.
  • a manufacturing method for a pharmaceutical container in which the pharmaceutical container is manufactured using the glass tube for a pharmaceutical container described above.
  • FIG. 1 is a graph showing an analysis result of concentration distribution of Na 2 O in the vicinity of a surface of Sample No. 25.
  • FIG. 2 is a graph showing an analysis result of concentration distribution of Na 2 O in the vicinity of a surface of Sample No. 32.
  • FIG. 3 is a graph showing a result of hydrolytic resistance test before and after a thermal treatment.
  • a borosilicate glass for a pharmaceutical container according to the invention includes SiO 2 , Al 2 O 3 , B 2 O 3 , and R 2 O (R is one or more kinds selected from Li, Na, and K) as essential components.
  • the borosilicate glass for a pharmaceutical container according to the invention does not substantially include BaO.
  • a glass composition includes BaO, crystals may be precipitated or a precipitate may be generated due to a reaction with an alumina-based refractory or a reaction between Ba ions extracted from the glass and sulfate ions in an aqueous-based medicament as described above.
  • the glass for a pharmaceutical container according the invention has 0.3/mm to 0.8/mm, 0.35/mm to 0.80/mm, and 0.4/mm to 0.75/mm of a water content in glass in terms of ⁇ -OH value.
  • 0.45/mm to 0.70/mm of the water content is preferable.
  • a ⁇ -OH value is excessively low, since absorption of infrared ray is small, heat of the burner is difficult to be transmitted, and it is necessary to convert with intense heat at the time of converting, which cause an alteration of an inner surface of the container.
  • the ⁇ -OH value is excessively high, glass excessively absorbs infrared ray to rapidly heated with a burner. Therefore, the glass is easily softened and deformed and it is difficult to maintain a shape of the container at the time of converting.
  • the ⁇ -OH value representing the water content in glass can be obtained using the following equation. In a case where the water content of a glass tube is measured, the measurement may be performed after dividing the glass tube in half.
  • ⁇ -OH value ⁇ log 10( T 1 /T 2 )
  • T 1 Transmittance (%) in the reference wavelength 3846 cm ⁇ 1 (2600 nm) of reference wavelength
  • T 2 Transmittance (%) in the hydroxyl group absorption wavelength 3600 cm ⁇ 1 (2800 nm).
  • a composition of borosilicate glass is not particularly limited, and it is preferable that the borosilicate glass includes 70.0% to 75.5% of SiO 2 , 6.3% to 11% of Al 2 O 3 , 3.0% to 11.5% of B 2 O 3 , 4.0% to 8.5% of Na 2 O, 0% to 5.0% of K 2 O, and 0% to 0.2% of Li 2 O in terms of mass % and substantially does not include BaO.
  • the borosilicate glass includes 65% to 80% of SiO 2 , 5% to 15% of Al 2 O 3 , 2% to 12% of B 2 O 3 , 3% to 10% of Na 2 O, 0% to 5% of K 2 O, 0% to 5% of Li 2 O, 0% to 5% of MgO, 0% to 5% of CaO, and 0% to 5% of SrO in terms of mass %, a value of Al 2 O 3 /(Na 2 O+K 2 O+Li 2 O+MgO+CaO+SrO+B 2 O 3 ) is 0.35 to 0.60 in terms of mass ratio, and the borosilicate glass substantially does not include BaO.
  • the expression “%” means mass %, unless otherwise noted.
  • SiO 2 is one of the components configuring a glass network.
  • the content of SiO 2 is 65% to 80% or 62% to 75.5%, preferably equal to or greater than 65% and smaller than 75.5%, equal to or greater than 67% and smaller than 75.5%, 70.0% to 75.5%, equal to or greater than 70.0% and smaller than 75.5%, or 70.0% to 75.0%, and particularly preferably 70.0% to 74.7%.
  • the content of SiO 2 is excessively small, chemical durability decreases, and acid resistance required for the borosilicate glass for a pharmaceutical container decreases.
  • the content of SiO 2 is excessively great, the liquidus viscosity decreases, devitrification easily occurs in the manufacturing step, thereby decreasing productivity.
  • Al 2 O 3 is a component which prevents devitrification of the glass and improves chemical durability and hydrolytic resistance.
  • the content of Al 2 O 3 is preferably 5% to 15%, 6.3% to 11%, 6.4% to 10%, or 6.5% to 8.5%, and particularly preferably 6.7% to 8.0%.
  • the content of Al 2 O 3 is excessively small, the effects described above are not obtained.
  • the viscosity of the glass increases and a working temperature increases. The quantity of heat required at the time of converting process into a pharmaceutical container increases.
  • B 2 O 3 has effects of not only decreasing a melting point of the glass, but also increasing a liquidus viscosity, and preventing devitrification. Accordingly, the content of B 2 O 3 is 2% to 12%, 3.0% to 11.5%, 5.5% to 11.4%, or 8.5% to 11.0%, and particularly equal to or greater than 9% and smaller than 11.0%. In a case where the content of B 2 O 3 is excessively small, a working temperature increases and quantity of heat required at the time of converting process into a pharmaceutical container increases. On the other hand, in a case where the content of B 2 O 3 is excessively great, hydrolytic resistance or chemical durability decreases.
  • Na 2 O has effects of decreasing viscosity of the glass and increasing a coefficient of linear thermal expansion.
  • the content of Na 2 O is preferably 3% to 10%, 3.2% to 8.5%, 3.5% to 8.5%, 4.0% to 8.5%, 4% to 8.3%, 4% to 8%, 4.2% to 8.4%, or 4.5% to 8.0%, and particularly preferably 5.0% to 7.0%.
  • a working temperature increases and quantity of heat required at the time of converting process into a pharmaceutical container increases.
  • hydrolytic resistance decreases.
  • K 2 O has effects of decreasing viscosity of the glass and increasing a coefficient of linear thermal expansion, in the same manner as Na 2 O.
  • the content of K 2 O is preferably 0% to 5%, 0.1% to 5%, 0.5% to 4.5%, or 1.0% to 3%, and particularly preferably 1.5% to 3.0%. In a case where the content of K 2 O is excessively great, hydrolytic resistance decreases.
  • K 2 O/Na 2 O is preferably 0.2 to 1, 0.20 to 0.95, or 0.2 to 0.8, and particularly preferably 0.2 to 0.7 in terms of mass ratio.
  • the ratio is small, hydrolytic resistance decreases.
  • the ratio is great, a working temperature increases and quantity of heat required at the time of converting process into a pharmaceutical container increases.
  • an amount of B 2 O 3 or Na 2 O evaporated at the time of converting process into a pharmaceutical container increases.
  • Li 2 O has effects of decreasing a viscosity of the glass and increasing a coefficient of linear thermal expansion, in the same manner as Na 2 O and K 2 O.
  • the content of Li 2 O is preferably 0% to 5%, 0% to 0.2%, 0% to 0.1%, or 0% to 0.05%, and particularly preferably 0% to 0.01%.
  • other alkali metal oxides other than Li 2 O are desirably used.
  • a total content of Li 2 O, Na 2 O, and K 2 O is preferably 5% to 10%, and particularly preferably 6% to 9%. In a case where the total content of these components is small, the working temperature increases. In addition, the total content of these components is great, chemical durability or hydrolytic resistance decreases.
  • MgO has an effect of improving chemical durability.
  • MgO has an effect of causing high-temperature viscosity of glass to be lowered.
  • the content of MgO is preferably 0% to 5%, 0% to 4.0%, 0% to 2.0%, 0% to 1.0%, or equal to or greater than 0% and smaller than 1%, and particularly preferably 0% to 0.5%. In a case where the content of MgO is excessively great, hydrolytic resistance decreases.
  • CaO has an effect of causing high-temperature viscosity of glass to be lowered.
  • the content of CaO is preferably 0% to 5%, 0% to 4.0%, 0% to 1.5%, 0% to 1.1%, equal to or greater than 0% and smaller than 1%, or 0% to 0.9% and particularly preferably 0% to 0.5%. In a case where the content of CaO is excessively great, hydrolytic resistance decreases.
  • SrO has an effect of improving chemical durability.
  • the content of SrO is preferably 0% to 5%, 0% to 4.0%, equal to or greater than 0% and smaller than 4%, or 0% to 2.0%, and particularly preferably 0% to 1.0%. In a case where the content of SrO is excessively great, hydrolytic resistance decreases.
  • a total content of MgO, CaO, and SrO is preferably 0% to 5%, 0% to 4.0%, 0% to 3.0%, 0% to 2.0%, or equal to or greater than 0% and smaller than 1.0%, and particularly preferably 0% to 0.5%.
  • the total content of these components is excessively great, high-temperature viscosity of glass can be lowered; however, hydrolytic resistance decreases.
  • a total content of MgO and CaO is preferably equal to or greater than 0% and smaller than 1% or 0% to 0.8%, and particularly preferably 0% to 0.5%.
  • the total content of these components is excessively great, hydrolysis characteristic decreases.
  • TiO 2 has an effect of improving hydrolytic resistance.
  • the content of TiO 2 is preferably equal to or greater than 0% and smaller than 7.0%, more preferably 0% to 5.0% or 0% to 4.0%, and particularly preferably 0% to 1.5%.
  • a working temperature increases and quantity of heat required at the time of converting process into a pharmaceutical container increases.
  • an amount of B 2 O 3 or Na 2 O evaporated at the time of converting process into a pharmaceutical container increases.
  • ZrO 2 has an effect of improving hydrolytic resistance.
  • the content of ZrO 2 is preferably equal to or greater than 0% and smaller than 7.0%, more preferably 0% to 5.0% or 0% to 4.0%, and particularly preferably 0% to 1.5%.
  • a working temperature increases and quantity of heat required at the time of converting process into a pharmaceutical container increases.
  • an amount of B 2 O 3 or Na 2 O evaporated at the time of converting process into a pharmaceutical container increases.
  • Fe 2 O 3 may cause coloring of glass to decrease transmittance in a visible range, and therefore, the content thereof is desirably equal to or smaller than 0.2%, equal to or smaller than 0.1%, and particularly desirably limited to be equal to or smaller than 0.02%.
  • One or more kinds of F, Cl, Sb 2 O 3 , SnO 2 , Na 2 SO 4 and the like may be included as fining agents.
  • the total content of these fining agents is equal to or smaller than 3%, preferably equal to or smaller than 1%, and more preferably equal to or smaller than 0.5%.
  • Cl or SnO 2 is preferably used in these fining agents, because the degree of effect on the melting temperature or the environment is small.
  • the content thereof is preferably equal to or smaller than 3%, more preferably equal to or smaller than 1%, and particularly preferably equal to or smaller than 0.2%.
  • SnO 2 the content thereof is preferably equal to or smaller than 2%, and more preferably equal to or smaller than 0.5%.
  • a value of (MgO+CaO+SrO)/(Na 2 O+K 2 O+Li 2 O) is adjusted to preferably equal to or smaller than 0.10, equal to or smaller than 0.08, or equal to or smaller than 0.07, and particularly preferably smaller than 0.07% in terms of mass ratio. In a case where this value is excessively great, hydrolytic resistance decreases.
  • a value of CaO/(Na 2 O+K 2 O+Li 2 O) is adjusted to preferably equal to or smaller than 0.10, more preferably equal to or smaller than 0.08, particularly preferably equal to or smaller than 0.07, and still more preferably smaller than 0.07 in teens of mass ratio. In a case where this value is excessively great, hydrolytic resistance decreases.
  • Al 2 O 3 which is a component causing hydrolytic resistance to improve but viscosity of glass to increase
  • Na 2 O, K 2 O, Li 2 O, MgO, CaO, SrO, and B 2 O 3 which are components causing the viscosity of a glass to decrease but hydrolytic resistance to decrease in a viewpoint of making hydrolytic resistance compatible with excellent processability.
  • Al 2 O 3 /(Na 2 O+K 2 O+Li 2 O+MgO+CaO+SrO+B 2 O 3 ) is preferably equal to or greater than 0.32, equal to or greater than 0.34, equal to or greater than 0.35, or equal to or greater than 0.36, and particularly preferably equal to or greater than 0.37 in terms of mass ratio.
  • a value thereof is equal to or smaller than 0.60, particularly equal to or smaller than 0.50.
  • Al 2 O 3 /(Na 2 O+K 2 O+Li 2 O+MgO+CaO+SrO+B 2 O 3 ) is a value obtained by dividing the content of Al 2 O 3 by a total content of Na 2 O, K 2 O, Li 2 O, MgO, CaO, SrO, and B 2 O 3 .
  • the value of Al 2 O 3 /(Na 2 O+K 2 O+Li 2 O+MgO+CaO+SrO+B 2 O 3 ) is excessively small, hydrolytic resistance of glass decreases.
  • the amount of B 2 O 3 or an alkali metal oxide component evaporated from the glass at the time of performing the converting with a burner increases.
  • Al 2 O 3 /(Na 2 O+K 2 O+Li 2 O) is 0.7 to 1.5 or 0.75 to 1.5, and particularly 0.75 to 1.2 in terms of mass ratio.
  • hydrolytic resistance decreases.
  • a working temperature increases and quantity of heat required at the time of converting process into a pharmaceutical container increases.
  • a value of (Na 2 O+K 2 O+Li 2 O—Al 2 O 3 )/B 2 O 3 is preferably equal to or smaller than 0.39, equal to or smaller than 0.37, or smaller than 0.36 in terms of a molar ratio.
  • the value thereof is 0.315 to 0.350, 0.320 to 0.345, 0.320 to 0.340, or equal to or greater than 0.325 and smaller than 0.340, and particularly equal to or greater than 0.33 and smaller than 0.340.
  • a content of alkali metal oxides such as Na 2 O, K 2 O, and Li 2 O is great, an amount of these evaporated due to various thermal treatments at the time of converting increases.
  • Na 2 O, K 2 O, Li 2 O, or B 2 O 3 is easily evaporated due to various thermal treatments at the time of converting and bubbles are easily generated in accordance with vaporization of water while chemical durability or hydrolytic resistance decreases. Or, a content of B 2 O 3 is great, and thus chemical durability or hydrolytic resistance decreases at the time before converting process to a container.
  • “Na 2 O+K 2 O+Li 2 O—Al 2 O 3 ” is a value obtained by subtracting a content of Al 2 O 3 from the total content of Na 2 O, K 2 O, and Li 2 O.
  • the borosilicate glass for a pharmaceutical container according to the invention preferably has the following characteristics.
  • the consumption of 0.02 mol/L hydrochloric acid per unit glass mass is preferably equal to or smaller than 0.030 mL, equal to or smaller than 0.028 mL, or equal to or smaller than 0.026 mL, and particularly preferably equal to or smaller than 0.025 mL.
  • the amount of glass components, particularly alkali metal components extracted may significantly increase to cause alteration of aqueous-based medicament components, at the time of manufacturing a pharmaceutical container such as an ampule or a vial, filling the pharmaceutical container with an aqueous-based medicament, and storing the aqueous-based medicament.
  • a weight loss per unit area is preferably equal to or smaller than 1.0 mg/dm 2 and particularly preferably equal to or smaller than 0.8 mg/dm 2 .
  • the amount of glass components extracted may significantly increase to cause alteration of aqueous-based medicament components, at the time of manufacturing a pharmaceutical container such as an ampule or a vial, filling the pharmaceutical container with an aqueous-based medicament, and storing the aqueous-based medicament.
  • the working temperature is equal to or lower than 1250° C., 1150° C. to 1250° C., more preferably 1150° C. to 1240° C., and particularly preferably 1160° C. to 1230° C.
  • a converting temperature in a case of manufacturing a glass container such as an ampule or a vial from a glass tube increases, and the amount of B 2 O 3 or alkali metal oxides in the glass evaporated significantly increases.
  • the liquidus viscosity is preferably equal to or greater than 10 4.5 dPa ⁇ s, equal to or greater than 10 5.6 dPa ⁇ s, equal to or greater than 10 5.2 dPa ⁇ s, equal to or greater than 10 5.4 dPa ⁇ s, and particularly preferably equal to or greater than 10 5.6 dPa ⁇ s.
  • the liquidus viscosity decreases, devitrification easily occurs at the time of glass tube forming using a Danner method, and productivity decreases.
  • a coefficient of linear thermal expansion is an important parameter for thermal shock resistance of glass.
  • the coefficient of linear thermal expansion in a temperature range of 30° C. to 380° C. is preferably equal to or smaller than 58 ⁇ 10 ⁇ 7 /° C. or 45 to 58 ⁇ 10 ⁇ 7 /° C., and particularly preferably 48 to 55 ⁇ 10 ⁇ 7 /° C.
  • the glass tube for a pharmaceutical container according to the invention is preferable to have a compositions or characteristics described above.
  • a bend of a tube is preferably equal to or smaller than 6.0 mm or equal to or smaller than 5.0 mm, and particularly preferably equal to or smaller than 4.0 mm.
  • a position of the glass tube is not stable and unevenness in heating by flame of a burner occurs.
  • a temperature of a portion that is difficult to be heated increases to a predetermined temperature, a portion that is easily heated is maintained in a state of high temperature and an amount of B 2 O 3 or Na 2 O evaporated increases.
  • a time for forming one container also becomes long, and an efficiency of converting process to a container is remarkably degraded.
  • a thickness deviation of a glass tube is preferably equal to or smaller than 15% or equal to or smaller than 13%, and particularly preferably equal to or smaller than 10%.
  • a value thereof is excessively great, difference in heat capacity of each portion of the glass tube becomes great, and a temperature of the glass tube does not evenly increase with a burner at the time of converting process to a container.
  • a temperature of a portion of which a thickness is large and the heat capacity is large increases to a predetermined temperature, a portion of which a thickness is small and the heat capacity is small is maintained in a state of high temperature and an amount of B 2 O 3 or Na 2 O evaporated increases.
  • a time for forming one container also becomes long, and an efficiency of converting process to a container is remarkably degraded.
  • a value of (atomic concentration of Na)/(atomic concentration of Na+atomic concentration of Si) within a region from an inner surface of the glass tube to a depth of 200 nm is preferably equal to or greater than 0.01 and smaller than 0.5 or equal to or greater than 0.01 and smaller than 0.4, and particularly preferably equal to or greater than 0.01 and smaller than 0.3.
  • an amount of B 2 O 3 or an alkali metal oxide component evaporated from glass at the time of performing heating with a burner increases.
  • a value of (atomic concentration of Na)/(atomic concentration of Na+atomic concentration of Si) in a region from a surface of glass to a depth of 200 nm is excessively small, flakes become easily generated.
  • a value of (atomic concentration of Na)/(atomic concentration of Na+atomic concentration of Si) in a region from a surface of glass to a depth of 200 nm can be controlled by appropriately selecting a forming condition of a glass tube or a kind of a refractory contacting to glass.
  • an atomic concentration of Na and an atomic concentration of Si can be quantified using, for example, an X-ray photoelectron spectroscopy (ESCA).
  • ESA X-ray photoelectron spectroscopy
  • an absolute value of (X1 ⁇ X2) is preferably 0.1 to 0.3. In a case where a value thereof is not within the range described above, flakes become easily generated.
  • a composition, appropriate ranges of characteristics, reason for limitation, and the like of borosilicate glass configuring the glass tube for a pharmaceutical container according to the invention are as described above, and here, descriptions thereof are omitted.
  • a glass batch is prepared by mixing glass raw materials with each other, so as to have the glass composition described above.
  • the glass batch is continuously put into a melting furnace at 1550° C. to 1700° C., to be melted and clarified.
  • the obtained molten glass is drawn out in a tubular shape from a tip end portion of a rotating refractory, while winding the molten glass around the rotating refractory and blowing air from the tip end portion.
  • the drawn tubular glass is cut to have a predetermined length and a glass tube for a pharmaceutical container is obtained.
  • the glass tube obtained as described above is supplied for the manufacturing of a vial or an ampule.
  • An adjustment of a water content ⁇ -OH value) in glass may be performed by using hydrous raw materials or adjusting a melting temperature or glass flow rate.
  • An adjustment of a bend or a thickness deviation of a glass tube may be performed by adjusting a temperature distribution in a muffle furnace, the rotation speed of a sleeve and the like.
  • a content of Na 2 O in the vicinity of an inner surface of the obtained glass tube (and a glass container) can be reduced by selecting a material in which a content of Na 2 O is small or a material (including coating a surface of refractory with platinum and the like) in which Na 2 O component is difficult to be extracted from the surface, as refractory to be used.
  • a glass tube having desired characteristics can be obtained by appropriately selecting or combining these means.
  • the glass tube for a pharmaceutical container according to the invention is not limited to be manufactured by the Danner method, and may be manufactured by using an arbitrary method which is well known in the related art.
  • a bellow method or a down-draw method is also an effective method as the manufacturing method of the glass tube for a pharmaceutical container according to the invention.
  • Tables 1 and 2 show samples (Sample Nos. 1 to 16).
  • “ ⁇ R 2 O” indicates “K 2 O+Na 2 O+Li 2 O”
  • “ ⁇ RO” indicates “MgO+CaO+SrO”.
  • Sample Nos. 1 to 15 showed excellent chemical durability and hydrolytic resistance. In addition, it was found that every sample had a working temperature of equal to or lower than 1220° C. Regarding Sample Nos. 2 and 6 to 15 including Sn in the glass composition, in a case where extraction of Sn was evaluated by a hydrolytic resistance test, the amount of extraction of Sn was smaller than a lower detection limit in any case of the samples. In addition, regarding Sample Nos. 1 to 15, the ⁇ -OH value was in a predetermined range, and it was possible to efficiently heat glass at the time of converting process to a container with a burner. Therefore, it is considered that an amount of B 2 O 3 or Na 2 O evaporated does not increase in spite of not including BaO.
  • the measurement of the coefficient of linear thermal expansion was performed by using glass samples formed in a rod shape having a size of approximately 5 mm ⁇ 50 mm by a dilatometer in a temperature range of 30° C. to 380° C.
  • the measurement of a strain point, an annealing point, and a softening point was performed by a fiber elongation method.
  • a viscosity curve of glass was obtained from high-temperature viscosity obtained by a platinum ball pulling method and a viscosity calculation formula of Fulcher, and a temperature corresponding to viscosity of 10 4 dPa ⁇ s was obtained from the viscosity curve.
  • a platinum boat having a size of approximately 120 ⁇ 20 ⁇ 10 mm was filled with a crushed glass sample and was put into an electric furnace having a linear temperature gradient for 24 hours. After that, a crystal precipitation portion was specified by microscope observation, a temperature corresponding to the crystal precipitation portion was calculated from a temperature gradient graph of the electric furnace, and this temperature was set as the liquidus temperature.
  • a viscosity curve of glass was obtained from a strain point, an annealing point, a softening point, a working temperature, and a viscosity calculation formula of Fulcher, the viscosity of the glass at the liquidus temperature was calculated form this viscosity curve, and this viscosity was set as the liquidus viscosity.
  • the hydrolytic resistance test was performed by a method of crushing a sample by using a mortar and a pestle made of alumina, based on a glass grains test of EP 8.0.
  • the specific test procedure is as follows. A surface of a sample was carefully wiped with ethanol, the sample was crushed by using a mortar and a pestle made of alumina, and the sample was classified by using three stainless steel sieves respectively having an aperture of 710 ⁇ m, 425 ⁇ m, and 300 ⁇ m. The sample powder remaining on the sieves was crushed again and subjected to the same sieving operation. The sample powder remaining on the sieve having an aperture of 300 ⁇ m was washed with ethanol and put into a glass container such as a beaker.
  • the acid resistance test was performed by setting a sample surface area as 50 cm 2 , and a liquid amount of hydrochloric acid having a concentration of 6 mol/L which is an eluate as 800 mL, based on DIN12116.
  • the specific test procedure is as follows. First, a glass sample piece including surfaces, all of which are obtained by mirror polishing finish and having a total surface area of 50 cm 2 was prepared, and the sample was dipped in a solution obtained by mixing hydrofluoric acid (40 mass %) and hydrochloric acid (2 mol/L) so as to have a volume ratio of 1:9, as pretreatment, and stirred with a magnetic stirrer for 10 minutes.
  • the sample piece was extracted, ultrasonic cleaning for 2 minutes was performed with extra pure water three times, and then, ultrasonic cleaning was performed in ethanol for 1 minute twice. Then, the sample piece was dried in an oven at 110° C. for 1 hour and cooled in a desiccator for 30 minutes. A mass m 1 of the sample piece obtained as described above was measured with a precision of ⁇ 0.1 mg, and recorded. Then, 800 mL of hydrochloric acid having a concentration of 6 mol/L was put in a beaker made of quartz glass, and heated until the boiling occurs by using an electric heater, and the sample piece hung with a platinum line was put in the beaker and stored for 6 hours.
  • the amount of extraction of Sn was analyzed regarding a test solution after the hydrolytic resistance test by using an ICP emission spectrometry device (manufactured by Varian). The specific test procedure is as described below.
  • the sample solution after the hydrolytic resistance test was filtered with a membrane filter and collected with a centrifuge tube.
  • a standard solution of Sn (manufactured by Wako Pure Chemical Industries, Ltd.) was diluted so that the content of Sn becomes 0 mg/L, 0.05 mg/L, 0.5 mg/L, and 1.0 mg/L, and standard solutions were prepared.
  • a calibration curve was created from these standard solutions and the amount of extraction of Sn in the test solution was calculated.
  • a measurement wavelength of Sn was 189.925 nm.
  • the water content in the glass was measured as the following procedure. 20 mm ⁇ 30 mm ⁇ 1 mm of plate glass was converted from the manufactured glass, and both surfaces thereof were subjected to mirror polishing and finishing. The water content in the plate glass was obtained as follows. Transmittance of glass was measured using FT-IR, and a ⁇ -OH value was calculated from the following Equation 1.
  • T 1 Transmittance (%) in 3846 cm ⁇ 1 (2600 nm) of reference wavelength
  • T 2 Transmittance (%) in 3600 cm ⁇ 1 (2800 nm) of absorption wavelength due to hydroxyl group
  • Table 3 shows Sample Nos. 17 to 24.
  • a batch raw material that was mixed as compositions and characteristics shown in the table was continuously put into a melting furnace at 1550° C. to 1700° C. to be melted and clarified. Then, the obtained molten glass was supplied to Danner apparatus, and the glass was drawn out in a tubular shape such that an outer diameter is to be 20 mm and an inner diameter is to be 18 mm (target thickness of 1 mm). Further, the drawn tubular glass was cut to have length of 1500 mm and a glass tube for a pharmaceutical container was obtained.
  • the Danner apparatus includes refractory sleeve provided in a muffle furnace and a tube drawer that draws out glass.
  • the refractory sleeve is inclined obliquely downward and provided so as to rotate around the central axis of the sleeve.
  • the refractory sleeve is made by winding the molten glass supplied onto the sleeve to a surface of the sleeve and guiding toward a tip end of the sleeve while rotating and inclining of the sleeve.
  • An air blast hole is provided in the tip end of the sleeve. Air is supplied into glass drawn from the tip end of the sleeve so as to keep the glass to the tubular shape.
  • the tube drawer includes a pair of facing rollers. The tube drawer stretches the tubular glass separated from the tip end of the sleeve to have a predetermined tube diameter by nipping the tubular glass with the rollers.
  • the glass tube samples obtained as described above were supplied for various evaluations.
  • a bend or a thickness deviation of the glass tube was controlled by changing a temperature distribution in a muffle furnace, a rotation speed of a sleeve, or the like.
  • Sample Nos. 17 to 22 showed excellent chemical durability and hydrolytic resistance. In addition, it was found that every sample had a working temperature of equal to or lower than 1220° C. Regarding Sample Nos. 17, 18, and 20 including Sn in the glass composition, in a case where extraction of Sn was evaluated by a hydrolytic resistance test, the amount of extraction of Sn was smaller than a lower detection limit in any case of the samples. In addition, regarding Sample Nos. 17 to 22, the bend and thickness deviation were in a predetermined range, and it was possible to efficiently heat the glass at the time of converting process to a container with a burner. Therefore, it is considered that an amount of B 2 O 3 or Na 2 O evaporated does not increase in spite of not including BaO.
  • the measurement of the bend of the glass tube was performed as the following procedure. On a flat plate, one end of the glass tube cut to 1000 mm was rotated while pressing, and the maximum value of height separated from the flat plate was measured.
  • the measurement of the thickness deviation of the glass tube was performed as the following procedure.
  • the glass tube was cut to 50 mm, and the thickness of the glass tube was measured while rotating the glass tube.
  • the thickness deviation was calculated using Equation 2.
  • the water content in the glass was measured as the following procedure. After dividing the manufactured glass tube in half, transmittance of the glass tube was measured using FT-IR, and a ⁇ -OH value was calculated from the following Equation 1.
  • T 1 Transmittance (%) in 3846 cm ⁇ 1 (2600 nm) of reference wavelength
  • T 2 Transmittance (%) in 3600 cm ⁇ 1 (2800 nm) of absorption wavelength due to hydroxyl group
  • Table 1 shows Sample Nos. 25 to 32.
  • FIGS. 1 and 2 show analysis results of (atomic concentration of Na)/(atomic concentration of Na+atomic concentration of Si) within a region from a surface of glass to a depth of 200 nm.
  • FIG. 1 shows an analysis result of Sample No. 32 and
  • FIG. 2 shows an analysis result of Sample No. 25.
  • a glass batch was prepared by mixing glass raw materials with each other, so as to have compositions and characteristics as shown in the table.
  • the glass batch was continuously put into a melting furnace at 1550° C. to 1700° C., to be melted and clarified.
  • the obtained molten glass was supplied to Danner apparatus.
  • the glass was drawn out in a tubular shape from a tip end portion of a rotating refractory (refractory sleeve), while winding the molten glass around the rotating refractory and blowing air from the tip end portion.
  • the drawn tubular glass was cut to have a predetermined length and a glass tube was obtained.
  • the glass tube obtained as described above was supplied for various evaluations. Table 4 shows the results thereof.
  • FIGS. 1 and 2 show a change amount of (atomic concentration of Na)/(atomic concentration of Na+atomic concentration of Si) of an inner surface of the glass tube of Sample Nos. 32 and 25.
  • the value of (atomic concentration of Na)/(atomic concentration of Na+atomic concentration of Si) of an inner surface of the glass tube was controlled by changing a kind of refractory used at the time of tube drawing and forming or a coating area of platinum film which was formed on a surface of refractory sleeve.
  • Sample Nos. 25 to 30 showed excellent hydrolytic resistance and chemical durability.
  • “Na/Na+Si” that indicates the maximum value of (atomic concentration of Na)/(atomic concentration of Na+atomic concentration of Si) within a region from a surface of glass to a depth of 200 nm
  • ” that indicates an absolute value of a difference of (atomic concentration of Na)/(atomic concentration of Na+atomic concentration of Si) between the inner surface of the glass tube and a region at a depth of 200 nm from the inner surface of the glass tube were equal to or smaller than 0.3.
  • extraction of Na ions was not observed.
  • Sample No. 32 has excellent hydrolytic resistance; however, an amount of extraction of Na ions from the inner surface of the glass tube is large and a change in pH was easily generated.
  • Sample No. 32 has low hydrolytic resistance, and there was a concern that it was not possible to reduce an amount of B 2 O 3 or Na 2 O evaporated during converting process to a container with a burner.
  • Na/Na+Si that indicates the maximum value of (atomic concentration of Na)/(atomic concentration of Na+atomic concentration of Si) within a region from a surface of glass to a depth of 200 nm
  • that indicates an absolute value of a difference of (atomic concentration of Na)/(atomic concentration of Na+atomic concentration of Si) between the inner surface of the glass tube and a region at a depth of 200 nm from the inner surface of the glass tube were analyzed as follows. The glass tube to be a sample was cut into a semicircular shape (divided into in half), and then a depth profile from the surface of the glass tube to a depth of 200 nm was prepared using an X-ray photoelectron spectroscopy. Analysis elements were Si and Na.
  • the glass tube was cut to have a length of 5 to 10 mm, a simple container which was prepared by sealing one side with a rubber stopper was filled with water, and covered with aluminum foil. After that, an extraction test based on EP 8.0 was performed. Methyl red was dropped to eluate and water and color comparison was performed. In a case where the color of methyl red of the eluate changes, it is determined that the Na ions are extracted, the evaluation result was indicated by “x”, and there was no change, it was determined that the Na ions are not extracted, the evaluation result was indicated by “0”.
  • each sample was subjected to thermal treatment in an electric furnace for five hours respectively at 600° C. and 900° C. It is assumed that the temperatures of 600° C. and 900° C. are temperatures of thermal treatment after converting.
  • the hydrolytic resistance test was carried out. An amount of extraction of Na ions, K ions, and Ca ions in the obtained eluate was measured. The smaller amount of extraction Na ions, K ions, and Ca ions, the higher the resistance to hydrolysis is meant.
  • Table 2 shows a total amount of extraction of each ions.
  • FIG. 3 shows an evaluation result for each thermal treatment. Regarding Sample No.
  • the borosilicate glass (glass tube) for a pharmaceutical container according to the invention can be suitably used as a material for various pharmaceutical containers such as an ampule, a vial, a prefilled syringe, and a cartridge.

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JP2015-173791 2015-09-03
JP2015173791A JP2017048091A (ja) 2015-09-03 2015-09-03 医薬容器用ホウケイ酸ガラス
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JP2015-207709 2015-10-22
JP2015207709A JP6653076B2 (ja) 2015-10-22 2015-10-22 医薬容器用ガラス管及びその製造方法
PCT/JP2016/075135 WO2017038738A1 (fr) 2015-09-03 2016-08-29 Verre borosilicate pour récipients de médicament, tube en verre pour récipients de médicament et procédé de production d'un conteneur de médicament

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US20200390978A1 (en) * 2019-06-13 2020-12-17 Schott Schweiz Ag Container which can be prefilled or is prefilled with fluid, as well as a cannula assembly and closure system for a container which can be prefilled or is prefilled with fluid
US20210380460A1 (en) * 2020-06-04 2021-12-09 Gerresheimer Bünde Gmbh Method and System for Producing a Glass Container as Well as Said Container
US11427497B2 (en) * 2019-11-08 2022-08-30 Schott Ag Toughenable glass with high hydrolytic resistance and reduced color tinge
US11642280B2 (en) * 2020-11-10 2023-05-09 Corning Incorporated Glass containers and sealing assemblies for maintaining seal integrity at low storage temperatures
US11834369B2 (en) 2018-08-13 2023-12-05 Corning Incorporated Ion exchangeable borosilicate glass compositions and glass articles formed from the same
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WO2020138063A1 (fr) * 2018-12-27 2020-07-02 日本電気硝子株式会社 Verre pour récipient de médicament, et tube en verre pour récipient de médicament et récipient de médicament l'utilisant
CN110272205A (zh) * 2019-06-26 2019-09-24 醴陵旗滨电子玻璃有限公司 一种硼硅酸盐玻璃及其制备方法和应用
EP3907198A1 (fr) 2020-05-06 2021-11-10 Schott Ag Tube de verre
CN112551891B (zh) * 2020-11-19 2022-10-14 江苏通鹏新材料研究院有限公司 玻璃组合物、玻璃管及其制备方法和应用

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US11834369B2 (en) 2018-08-13 2023-12-05 Corning Incorporated Ion exchangeable borosilicate glass compositions and glass articles formed from the same
US20200390978A1 (en) * 2019-06-13 2020-12-17 Schott Schweiz Ag Container which can be prefilled or is prefilled with fluid, as well as a cannula assembly and closure system for a container which can be prefilled or is prefilled with fluid
US11865319B2 (en) * 2019-06-13 2024-01-09 Schott Pharma Schweiz Ag Container which can be prefilled or is prefilled with fluid, as well as a cannula assembly and closure system for a container which can be prefilled or is prefilled with fluid
US11427497B2 (en) * 2019-11-08 2022-08-30 Schott Ag Toughenable glass with high hydrolytic resistance and reduced color tinge
US20210380460A1 (en) * 2020-06-04 2021-12-09 Gerresheimer Bünde Gmbh Method and System for Producing a Glass Container as Well as Said Container
US11642280B2 (en) * 2020-11-10 2023-05-09 Corning Incorporated Glass containers and sealing assemblies for maintaining seal integrity at low storage temperatures
US11963928B2 (en) 2021-09-30 2024-04-23 Corning Incorporated Glass containers for storing pharmaceutical compositions
US11963929B2 (en) 2021-09-30 2024-04-23 Corning Incorporated Glass containers for storing pharmaceutical compositions

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EP3345876A1 (fr) 2018-07-11
WO2017038738A1 (fr) 2017-03-09
CN107949547A (zh) 2018-04-20
EP3345876A4 (fr) 2019-06-19

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